Doping of nitrogen and sulfur on biochar (NS-B) was investigated by a novel and improved method for diethyl phthalate (DEP) removal. The preparation parameters including pyrolysis temperature and size of peanut shell biochar as well as thiourea/biochar mass ratio were selected as independent variables at three levels by applying the Box-Behnken design. The ANOVA results indicated that thiourea/biochar mass ratio exhibited the most significant effect. The comprehensive effects of the three factors on DEP removal efficiency were further elaborated, combining with the characterization results of the obtained NS-B materials. The formation of the pyridinic N and oxidized S groups examined by XPS was responsible for enhancing the DEP removal efficiency. The adsorption kinetic model fitting illustrated that large micropores and numerous adsorption sites improved the adsorption capacity of NS-B. According to the adsorption isotherm model fitting, NS-B (temperature 375 °C, size 300 mesh and thiourea/biochar mass ratio 0.1) possessed much higher maximum adsorption capacity for DEP (14.34 mg g⁻¹) than biochar (6.57 mg g⁻¹). NS-B exhibited excellent reusability towards DEP removal after five times recycling. Moreover, NS-B also had the potential in peroxydisulfate activation. These findings provide new insights into the environmental implications of NS-B.

Heavy metal pollution is very common in soils. Soils are complex systems including minerals, bacteria, and various other substances. In Cd(II) contaminated soil, the combined effects of clay minerals and heavy metals on bacterial biofilm and Cd(II) adsorption are unappreciated. Our study showed that the combination of clay minerals (goethite, kaolinite, and montmorillonite) and heavy metals promoted Serratia marcescens S14 biofilm development significantly more than clay minerals or Cd(II) alone. The amount of biofilm after binary treatment with clay minerals and Cd(II) was 2.3–7.3 times than that in control. Mineral-induced cell death and the expression of the fimA, bsmA, and eps were key players in biofilm formation. Binary treatment with montmorillonite and Cd(II) significantly enhanced biofilm development and consequently increased the adsorption of Cd(II). Cd(II) removal is the result of co-adsorption of bacteria and minerals. Bacterial biofilm played an important role in Cd(II) adsorption. FTIR spectroscopy showed the components of biofilm were not affected by minerals and revealed the functional groups –OH, –NH, –CH₂, –SH, –COO participated in Cd(II) immobilization. Our findings are of fundamental significance for understanding how minerals and Cd(II) affect biofilms and thereby enhance Cd(II) adsorption and predicting the mobility and fate of heavy metals in heavy metal-contaminated soil.

Cypermethrin is a frequently used insecticide in agriculture and households but its chronic and molecular effects are poorly known are . Here we describe effects of sublethal cypermethrin exposure on the global transcriptome in the brain of honey bees determined by RNA-sequencing. Exposure for 48 h to 0.3 ng/bee cypermethrin (3 ng/mL sucrose solution) causes 38 differentially expressed genes (DEGs), of which 29 are up-regulated and 9 down-regulated. Exposure to 3 ng/bee causes differential expression of 265 DEGs (209 up-, 56 down-regulated). Among the 24 DEGs shared by both concentrations are genes encoding muscular structure, muscular processes and esterase B1. Functional analysis (GO term analysis) confirms the enrichment of muscular development, structure and function among the 89 and 35 significantly altered GO terms at the low and high concentration, respectively. Up-regulation of nine DEGs determined by RT-qPCR showed a good correlation with RNA-sequence data. Among them are genes including esterase B1, titin, twitchin, mucin-19, insulin like growth factor binding protein, golgin like protein and helix loop protein. Our study demonstrates for the first time molecular effects of cypermethrin at environmental concentrations, which include expressional induction of genes encoding muscular and cellular processes and metabolism enzymes. Further studies should demonstrate the physiological consequences in bees.

Bees are considered as important providers of ecosystem services, acting via pollination process in crops and native plants, and contributing significantly to the maintenance of biodiversity. However, the decrease of bee's population has been observed worldwide and besides other factors, this collapse is also related to the extensive use of pesticides. In this sense, studies involving the assessment of adverse effects and the uptake of pesticides by bees are of great concern. This work presents an analytical method for the determination of the insecticide abamectin and the fungicide difenoconazole in the stingless bee Melipona scutellaris exposed via oral and topic to endpoints concentrations of active ingredients (a.i.) alone and in commercial formulations and the discussion about its mortality and uptake. For this purpose, QuEChERS (Quick, Easy, Cheap, Efficient, Rugged and Safe) acetate modified method was used for extraction and pesticides were determined by LC-MS/MS. The validation parameters have included: a linear range between 0.01 and 1.00 μg mL⁻¹; and LOD and LOQ of 0.038 and 0.076 μg g⁻¹ for abamectin and difenoconazole, respectively. The uptake of tested pesticides via oral and topic was verified by the accumulation in adult forager bees, mainly when the commercial product was tested. Mortality was observed to be higher in oral exposure than in topic tests for both pesticides. For abamectin in a commercial formulation (a.i.) no differences were observed for oral or topic exposure. On the other hand, for difenoconazole, topic exposure had demonstrated higher accumulation in bees, according to the increase of received dose. Through the results, uptake and the possible consequences of bioaccumulated pesticides are also discussed and can contribute to the knowledge about the risks involving the exposure of bees to these compounds.

Organophosphate esters (OPEs) are widely used as flame retardants, plasticizers and defoamers and their exposure are likely associated with a number of adverse effects in humans. In this study, tris(chloroethyl) phosphate and thirteen OPE metabolites including six hydroxylated OPEs (HO-OPEs) were analyzed in 46 urine samples, collected from 8 provinces located across different regions in China. 1-Hydroxy-2-propyl bis(1-chloro-2-propyl) phosphate (BCIPHIPP) and 2-hydroxyethyl bis(2-butoxyethyl) phosphate (BBOEHEP) were major metabolites of their parent compounds with detection frequencies of 54.3%–89.1%, which were all higher than their corresponding OPE diesters (2.2%–6.5%). The urine-based estimated daily intake (EDI) of OPEs ranged from 0.06 ng/kg·bw for tris(2-butoxyethyl) phosphate (TBOEP) to 273 ng/kg·bw for 2-ethylhexyl phenyl phosphate. Analyzed with concentrations in paired dust samples, dust exposure to OPEs and their diesters may explain 0.28%–23.8% of the urine-based EDI of OPEs and the contribution of dust TBOEP was the highest. Although direct exposure to OPE diesters in dust showed a minor contribution, their intake via food and drinking water may account for a larger portion of urinary OPE metabolites. Overall, the hazard quotients of four OPEs indicated no immediate exposure risk for the investigated Chinese residents but the cumulative and long-term chronic effects involving exposure to other OPEs and OPE diesters are worth further concerns.

The neonicotinoid imidacloprid (IMI) is one of the most extensively applied neuro-active insecticides worldwide and continues to enter surface waters in many countries despite a recent ban for outdoor use in the EU. Yet little is known about ecotoxicological effects on non-target benthic freshwater species exposed to environmentally relevant concentrations of IMI and its marketed products. The aim of the present study was to narrow this gap by assessing effects of pure IMI and its commercial formulation Confidor® on the aquatic oligochaete Lumbriculus variegatus, a key species in freshwater sediments. To this end, we determined dose-response relationships in 24 h toxicity tests, bioconcentration during 24 h and 5 d of exposure to 0.1, 1 and 10 μg IMI L⁻¹, and physiological stress responses by measuring glutathione S-transferase, glutathione reductase and catalase activity in the same conditions. Maximum neonicotinoid concentrations reported from the field were lethal to L. variegatus within 24 h (LC₅₀ of 65 and 88 μg IMI L⁻¹ in pure form and as active ingredient of Confidor®, respectively). At sub-lethal exposure concentrations, tissue content of IMI significantly increased with exposure time. The observed bioconcentration factors (BCFs) were far above the water octanol coefficient (KOW), indicating a potentially large underestimation of IMI bioaccumulation when based on KOW. Activities of biotransformation and antioxidant enzymes indicated attempts of L. variegatus to counter xenobiotic-triggered oxidative stress to very low IMI and Confidor® concentrations. Together, our data add significantly to growing evidence that the continued proliferation of neonicotinoids require increased efforts in environmental risk assessment, especially in view of species-specific differences in sensitivities to the insecticide and possibly to additives of commercial formulations.

Very little is currently known regarding the effects of estrogenic endocrine disrupting chemicals on embryonic and larval development in molluscs, nor the potential effects of parental (F₀) exposure on resultant F₁ offspring. In this study, we assessed the embryotoxic impacts of exposure to environmentally relevant concentrations of the synthetic estrogen, 17α-ethinylestradiol (EE2), to male and female parents (50 ng/L) and their offspring (5 and 50 ng/L) in the native Australian Sydney rock oyster, Saccostrea glomerata. There were no detectable effects of parental exposure on fertilisation success, proportions of early larval (F₁) morphs and unfertilised eggs. Offspring impacts were evidenced in terms of developmental delays, with decreased percentages of D-veligers retained by 45 μm mesh, along with a reduction of swimming capabilities of larvae at 2 days post-fertilisation (dpf) when both parents had been exposed to 50 ng/L EE2. Although no significant parental effects were found on the survival of F₁ larvae at 9 dpf, retardation of shell growth was observed on F₁ larvae in treatments where both parents had been exposed to 50 ng/L EE2. Subsequent larval exposure from 2 to 9 dpf caused declines in survival and reduction of shell length in F₁ larvae at both 5 and 50 ng/L EE2 across all parental exposure treatments. Collectively, parental EE2 imparts effects on offspring in terms of retardation of larval development, and subsequent offspring exposure to EE2 further exacerbates impacts to development. Future research should aim to understand the potential mechanisms of EE2 induced toxicity and its transmission resulting in altered phenotypes of the F₁ generation.

The present study proposes a maize sprouts hydroponic growth model to evaluate the As, Cd, Cr and Pb translocation from multinutrient fertilizer and to do speciation of As and Cr in this fertilizer and As in parts of plant in order to predict their phytoavailability. X-ray absorption near edge structure (XANES) was employed to speciate As and Cr directly on fertilizer solid sample. Arsenate (Asⱽ) and a solid solution of FeCrO₃ were the major species identified in the samples. The sprouts were hydroponically cultivated in water, fertilizer slurry and fertilizer extract media. Concentrations of As, Cd and Pb measured on leaves of maize sprouts ranged from 0.061 to 0.31 mg kg⁻¹, whereas Cr was not translocated to the aerial parts of sprouts. High performance liquid chromatographic with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) analysis was used to determine As speciation in maize sprouts, as well as in the fertilizer extracts and slurries. Arsenate was the only species identified in the initial fertilizer extract and this information is in agreement with the XANES results. However, the reduction of arsenate to arsenite was observed in extracts and slurries collected after sprout growth, probably due to the action of exudates secreted by plant roots. Arsenite was the predominant species identified in sprouts, the high phosphate concentration in the medium may have contributed to reduce arsenate phytoavailability.

Bacteria with arsenate-reducing (ars) and arsenite-oxidizing (aio) genes usually co-exist in aerobic environments, but their contrast impacts on arsenic (As) speciation and mobility remain unclear. To identify which kind of bacteria dominate As speciation under oxic conditions, we studied the biotransformation of adsorbed As on goethite in the co-existence of Pantoea sp. IMH with ars gene and Achromobacter sp. SY8 with aio gene. The incubation results show that SY8 dominated the dissolved As speciation as As(V), even though aio exhibited nearly 5 folds lower transcription levels than ars in IMH. Nevertheless, our XANES results suggest that SY8 showed a negligible effect on solid-bound As speciation whereas IMH reduced adsorbed As(V) to As(III). The change in As speciation on goethite surfaces led to a partial As structural change from bidentate corner-sharing to monodentate corner-sharing as evidenced by our EXFAS analysis. Our Mössbauer spectroscopic results suggest that the incubation with SY8 reduced the degree of crystallinity of goethite, and the reduced crystallinity can be partly compensated by IMH. The changes in As adsorption structure and in goethite crystallinity had a negligible effect on As release. The insights gained from this study improve our understanding of biotransformation of As in aerobic environment.

The investigation of microplastics (MPs) in freshwater has received increased attention within the last decade. To date, sampling is mainly conducted at the surface of both rivers and lakes and only a few studies assessed the vertical distribution of MPs in the water column of freshwater bodies. To contribute to the understanding of MP pollution in the water column of freshwater lakes, this study evaluated the vertical profile of MPs in Lake Tollense considering particles between 63 and 5000 μm in size. Sampling was conducted on three occasions at three depths (surface, 7 m and 10 m) along a transect including eight sampling stations. The retrieved samples were digested with hydrogen peroxide and sodium hypochlorite and investigated via Nile Red staining and fluorescence microscopy. Subsequently, a sub-sample of stained particles was verified by μRaman-spectroscopy. The vertical distribution of MPs in Lake Tollense differed considerably between particle shapes (irregular particles (IPs) and fibers). Fibers did not show a noticeable pattern with depth and ranged between 22 fibers m⁻³ at 0 m to 19 fibers m⁻³ at 10 m. In contrast, IPs were distinctly less abundant in sub-surface samples with concentrations between 50 IPs m⁻³ at 0 m to 29 IPs m⁻³ at 10 m. Concerning IPs, buoyant polymers (mainly PE and PP) and concerning fibers PET and PP dominated the polymeric composition. Besides particle inherent properties, wind-induced mixing is likely affecting the intensity of vertical concentration gradients. This study highlights the need for depth-integrated sampling approaches in order to achieve representative data without over- or underestimating the overall abundances.